Control of phytopathogens using dinitroaniline compounds

ABSTRACT

It has been discovered that fungal foliar phytopathogens may be controlled by the use of a broad class of 2,6-dinitroanilines. The fungicidally-effective compounds may bear a broad range of substituent groups on the anilino nitrogen and in the 3- and 4-positions of the benzene ring.

CROSS REFERENCE

This application is a division of application Ser. No. 878,370, filedFeb. 16, 1978, now U.S. Pat. No. 4,180,568, Dec. 25, 1979; which was adivision of application Ser. No. 719,299, filed Aug. 31, 1976, now U.S.Pat. No. 4,091,096, May 23, 1978; which was a continuation-in-part ofapplication Ser. No. 668,360, filed Mar. 19, 1976, now abandoned; whichwas a continuation-in-part of application Ser. No. 589,312, filed June23, 1975, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the control of plant pathogens. Moreparticularly, this invention relates to the control of fungal foliarphytopathogens, especially downy mildew and late blight, using a broadclass of 2,6-dinitroanilines.

2. Description of the Prior Art

Beginning in the early 1960's, Soper disclosed that 2,6-dinitroanilinespossess herbicidal activity, most notably preemergent herbicidalactivity. See, for example, U.S. Pat. Nos. 3,111,403; 3,257,190;3,332,769; and 3,367,949. Following Soper's lead, a large number ofrelated dinitroanilines have also been shown to possess similarherbicidal activity. See, for example, U.S. Pat. Nos. 3,321,292;3,617,251; 3,617,252; 3,672,864; 3,672,866; 3,764,624; and 3,877,924 andBelgian Pat. No. 787,939. See also U.S. Pat. No. 3,725,479, forintermediate compounds.

Malichenko et al., Fiziol. Aktiv. Veschestva 1969, 2, 75-8; C.A. 73,13451e (1970), disclose that some 2,6-dinitroanilines bearing atrifluoromethyl group in the 4-position possess some activity againstPhytophthora infestans, the causative organism of late blight oftomatoes.

Clark et al., U.S. Pat. No. 3,119,736, disclose a broad class ofcompounds alleged to be fungicides. The generic description of suchcompounds includes dinitroanilines, but there is no specific disclosureof 2,6-dinitroanilines.

Zsolnai, Biochemical Pharmacology 5, 287-304 (1961), discloses thatcertain 2,4-dinitroanilines possess some fungicidal activity againstvarious organisms. No 2,6-dinitroaniline was disclosed, nor wasPlasmopara viticola among the organisms against which activity wasshown.

Buczacki, Ann. Appl. Biol. 75, 25 (1973), tested five dinitroanilinesagainst clubroot of cabbage with variable results. He concluded,however, that "dinitroanilines are unlikely to be of value in thecontrol of clubroot."

Eshel and Katan, Weed Science 20, 243 (1972), observed the effects offour dinitroanilines against Rhizoctonia solani and Fusarium oxysporum.Three of the four test compounds decreased the growth of R. solani atthe highest rates tested, but none of the four appreciably decreased thegrowth of F. oxysporum at any rate tested.

A study of trifluralin-treated soil by Breazeale and Camper, Appl.Microbiol. 19, 379 (1970), indicated that the actinomycete populationincreased as compared to the control, while the population of bacteriaand fungi decreased.

A discussion of tests against the fungus Lagenidium callinectes ispresented by Bland et al. in a paper entitled "Chemical Control ofLagenidium," an SEA Grant Publication UNC-SG-76-02, March 1976. Thepublication shows that some control of the fungus, which is a parasiteof marine crustacea, is accomplished by application of TREFLAN(trifluralin) to water in which spores of the fungus were growing.

SUMMARY OF THE INVENTION

The present invention is a method for reducing the incidence andseverity of fungal foliar phytopathogens. Use of the method for thecontrol of downy mildew and of late blight are preferred embodiments ofthe invention. The method is performed by applying to the foliage of thehost plant a fungicidally-effective amount of a 2,6-dinitroanilineselected from the class consisting of compounds having the followingformulae: ##STR1## wherein R¹ is H, C₂ -C₃ alkyl, chloroethyl,cyanoethyl, C₃ -C₄ alkenyl or halo C₃ -C₄ alkenyl;

when R¹ is H, R² is N(R³)₂, normal C₃ -C₆ alkyl, branched C₄ -C₇ alkylcontaining no tertiary carbon atoms, 1-hydroxy-2-propyl, methallyl,N-ethyl-3-piperidyl, 2,6-dimethyl-1-piperidyl, 2,5-dimethylpyrrolidinoor 2-ethyl-1-piperidyl;

when R¹ is not H, R² is 3-chloro-n-butyl, C₃ -C₄ alkenyl, halo C₃ -C₄alkenyl, chloroethyl, cyclopropylmethyl, cyanoethyl, hydroxyethyl, n-C₃H₇, or epoxypropyl;

each R³ is independently C₁ -C₃ alkyl; ##STR2## wherein

R⁴ is H or C₁ -C₃ alkyl;

when R⁴ is H, R⁵ is N(R⁶)₂, C₁ -C₇ normal or branched alkyl containingno tertiary carbon atoms, C₃ -C₄ alkenyl or N-methyl-2-propionamido;

when R⁴ is C₁ -C₃ alkyl, R⁵ is C₁ -C₄ alkyl or C₃ -C₄ alkenyl; and

each R⁶ is independently C₁ -C₃ alkyl; ##STR3## wherein

R⁷ is H, CN, C₁ -C₃ alkyl or C₂ -C₃ alkanoyl;

R⁸ is H or C₁ -C₃ alkyl;

where R⁸ is H, R⁹ is N(R¹⁰)₂, C₁ -C₆ normal or branched alkyl containingno tertiary carbon atoms, or C₃ -C₄ alkenyl;

when R⁸ is C₁ -C₈ alkyl, R⁹ is C₁ -C₃ alkyl, halo C₃ -C₄ alkenyl,propargyl, tetrahydrofurfuryl or C₃ -C₄ alkenyl; and

each R¹⁰ is independently C₁ -C₃ alkyl; ##STR4## wherein

R¹¹ is H or C₁ -C₃ alkyl;

when R¹¹ is H, R¹² is N(R¹³)₂, C₁ -C₄ normal or branched alkylcontaining no tertiary carbon atoms, or C₃ -C₄ alkenyl;

when R¹¹ is C₁ -C₃ alkyl, R¹² is C₁ -C₃ alkyl or C₃ -C₄ alkenyl; and

each R¹³ is independently C₁ -C₃ alkyl; ##STR5## wherein

X is N(R¹⁶)₂, chloro, CH₃, N═S(R¹⁷)₂, N(R¹⁸)CH₂ Het, C₁ -C₂ alkoxy,N═CHN(CH₃)₂, N═C(R¹⁹)OR²⁰, N═CHOR²¹ or N₃ ;

R¹⁴ is H, C₃ -C₄ alkenyl or C₁ -C₄ alkyl;

when R¹⁴ is H, R¹⁵ is C₃ -C₇ secondary alkyl;

when R¹⁴ is not H, R¹⁵ is C₁ -C₅ alkyl, cyclopropylmethyl, C₅ -C₆cycloalkyl, C₃ -C₄ alkenyl, halo C₂ -C₃ alkyl or halo C₃ -C₄ alkenyl;

one of R¹⁶ is H or CH₃ and the other is H, SCCl₃, CH₃, phenylthio, OH,C₁ -C₄ alkoxy or NH₂ ;

each R¹⁷ is independently C₁ -C₂ alkyl, phenyl or benzyl;

Het is 2,5-dimethylpyrrolidino, piperidino, morpholino, C₁ -C₂alkylpiperidino, hexahydroazepino, 2,2-dimethylaziridino, or C₁ -C₂alkylpiperazino;

R¹⁸ is H or methyl;

R¹⁹ is C₁ -C₂ alkyl or phenyl;

R²⁰ is C₁ -C₄ alkyl; and

R²¹ is C₁ -C₂ alkyl; ##STR6## wherein

R²² is cyano C₁ -C₃ alkyl, halo or C₁ -C₄ alkyl;

R²³ is H, chloroethyl, hydroxyethyl or C₁ -C₄ nontertiary alkyl; and

when R²³ is H, R²⁴ is C₃ -C₇ secondary alkyl;

when R²³ is not H, R²⁴ is C₁ -C₄ nontertiary alkyl, chloroethyl,hydroxyethyl, halo C₃ -C₄ alkenyl or C₃ -C₄ alkenyl; ##STR7## wherein

Y is H or CH₃ ;

Z is NH₂, SCH₂ CN, Cl, CH₃ or OCH₃ ;

R²⁵ is H or C₂ -C₄ nontertiary alkyl; and when R²⁵ is H, R²⁶ is C₃ -C₇secondary alkyl or N-methyl-2-propionamido;

when R²⁵ is C₂ -C₄ nontertiary alkyl, R²⁶ is C₂ -C₄ nontertiary alkyl orC₃ -C₄ alkenyl; ##STR8## wherein

Q is OH, OCH₃, SCH₃, SCN, SCH₂ CH₂ CN, SCH₂ CN, SCH₂ CO₂ CH₃, CO₂ H,CONH₂ or CN;

R²⁷ is H or C₁ -C₃ alkyl; and

when R²⁷ is H, R²⁸ is N(CH₃)₂ or C₁ -C₆ normal or branched alkylcontaining no tertiary carbon atoms; and

when R²⁷ is C₁ -C₃ alkyl, R²⁸ is propargyl, tetrahydrofurfuryl or C₁ -C₄nontertiary alkyl; ##STR9## wherein

R²⁹ is hydrogen, C₃ -C₄ alkenyl or C₁ -C₃ alkyl;

when R²⁹ is hydrogen, R³⁰ is C₃ -C₇ secondary alkyl;

when R²⁹ is not hydrogen, R³⁰ is C₁ -C₄ alkyl; and n is 0 or 1.

A particularly preferred embodiment of the invention is the method forreducing the incidence and severity of grape downy mildew whichcomprises applying to the foliage of the host plant afungicidally-effective amount of a compound described above.

Another particularly preferred embodiment is the method for reducing theincidence and severity of tomato late blight when comprises applying tothe foliage of the host plant a fungicidally-effective amount of adinitroaniline compound of the formula ##STR10## wherein

X' is N(R³³)₂, chloro, CH₃, N═S(R³⁴)₂,N(R³⁵)CH₂ Het', C₁ -C₂ alkoxy,N═CHN(CH₃)₂, N═C(R³⁶)OR³⁷, N═CHOR³⁸ or N₃ ;

R³¹ is H, C₃ -C₄ alkenyl or C₁ -C₄ alkyl;

when R³¹ is H, R³² is C₃ -C₇ secondary alkyl;

when R³¹ is not H, R³² is C₁ -C₅ alkyl, cyclopropylmethyl, C₅ -C₆cycloalkyl, C₃ -C₄ alkenyl, halo C₂ -C₃ alkyl or halo C₃ -C₄ alkenyl;

one of R³³ is H or CH₃ and the other is H, SCCl₃, CH₃, phenylthio, OH,C₁ -C₄ alkoxy or NH₂ ;

each R³⁴ is independently C₁ -C₂ alkyl, phenyl or benzyl;

Het' is 2,5-dimethylpyrrolidino, piperidino, morpholino, C₁ -C₂alkylpiperidino, hexahydroazepino, 2,2-dimethylaziridino, or C₁ -C₂alkylpiperazino;

R³⁵ is H or methyl;

R³⁶ is C₁ -C₂ alkyl or phenyl;

R³⁷ is C₁ -C₄ alkyl; and

R³⁸ is C₁ -C₂ alkyl.

It will be noted that the above formula is equivalent to Formula Vabove.

DESCRIPTION OF THE PREFERRED EMBODIMENT

For the most part, the 2,6-dinitroanilines useful in the method of thisinvention are compounds known in the herbicide art. Exceptions of thisgeneral rule are the 3-azido compounds of Formula II; the cyanamines ofFormula III; the cyanomethylthio compound of Formula VII; some of thesulfur-containing compounds of Formula VIII; and the sulfenamides andsulfinamides of Formula IX, all of which are new compounds firstsynthesized by us.

Those compounds useful in this invention which are known in theherbicide art are prepared by methods described in the various patentslisted in the prior art section of this specification and all of whichare incorporated herein by reference. Since the preparative proceduresdescribed in such patents are sufficient to allow those skilled in theart to prepare the compounds, no attempt will be made here to furtherdescribe the preparation of such compounds.

The 3-azido compounds of Formula II, the cyanamines of Formula III andthe sulfur-containing compounds of Formula VIII are prepared from thecorresponding 3-chloro compounds. The 3-chloro compounds areintermediates in the preparation of the 1,3-phenylenediamines of U.S.Pat. No. 3,617,252 and the 3-alkoxy and alkylthio compounds of U.S. Pat.No. 3,764,624 and the preparation of the 3-chloro intermediates isdescribed in both such patents.

The 3-azido compounds are prepared, for example, by the reaction of thecorresponding 3-chloro compound with an alkali metal azide such assodium azide in the presence of an inert solvent such asdimethylformamide. The reaction is conveniently run at room temperature.The 3-thiocyanato compounds are prepared in a similar manner employingan alkali metal sulfide such as sodium sulfide and cyanogen chloride.Compounds bearing a cyanomethylthio group in the 3-position are preparedfrom the corresponding 3-chloro compound by reaction with sodium sulfideand chloroacetonitrile. The other sulfur-containing compounds areprepared by reaction of the 3-chloro compound with the appropriatemercapto compound in the presence of an alkali metal hydroxide such aslithium hydroxide or potassium hydroxide. The cyanamines are prepared byheating the 3-chloro intermediate with cyanamide in the presence of atertiary amine such as triethylamine.

While it is believed that those skilled in the art can prepare all thecompounds useful in the present invention, the following preparativeexamples are given to insure that the novel compounds described abovecan be readily prepared.

EXAMPLE 1

A solution of 2.3 g. of sodium azide in 15 ml. of water was addeddropwise to a solution of 7 g. of3-chloro-N,N-dimethyl-2,6-dinitro-4-trifluoromethylaniline in 90 ml. ofdimethylformamide at room temperature. The mixture was stirred at roomtemperature for one hour, poured over ice-water and filtered to recover6.9 g. (94%) of3-azido-N,N-dimethyl-2,6-dinitro-4-trifluoromethylaniline, m.p. 66°-67°C. The structure was confirmed by the NMR and IR spectra and elementalanalysis.

Calculated: C, 33.76; H, 2.20; N, 26.25; Found: C, 33.98; H, 2.19; N,26.53.

EXAMPLE 2

A solution of 0.75 g. of sodium azide in 15 ml. of water was addeddropwise to a solution ofN-n-butyl-3-chloro-2,6-dinitro-N-ethyl-4-trifluoromethylaniline in 75ml. of dimethylformamide at room temperature. The mixture was stirred atroom temperature for 2 hours and poured over ice-water. The productseparated as an oil. The mixture was extracted three times withmethylene chloride, the methylene chloride was evaporated, the residuetaken up in ether, and the ether solution extracted three times withwater. Evaporation of the ether left 3.1 g. (92%) of3-azido-N-n-butyl-2,6-dinitro-N-ethyl-4-trifluoromethylaniline as anoil. The structure was confirmed by the NMR and IR spectra and elementalanalysis.

Calculated: C, 41.49; H, 4.02; N, 22.33; Found: C, 41.39; H, 3.89; N,22.10.

EXAMPLE 3

A solution of 1.0 g. of sodium azide in 10 ml. of water was addeddropwise to a solution of 3.2 g. ofN-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-N',N'-dimethylhydrazinein 80 ml. of dimethylformamide at room temperature. The mixture wasstirred at room temperature for one hour, poured over ice-water andfiltered. The solid product was dried and recrystallized from 2B ethanolto yield 3.1 g. (93%) ofN-(3-azido-2,6-dinitro-4-trifluoromethylphenyl)-N',N'-dimethylhydrazine,m.p. 123°-125° C. The structure was confirmed by the NMR and IR spectraand elemental analysis.

Calculated: C, 32.25; H, 2.41; N, 29.25; Found: C, 32.21; H, 2.39; N,29.34.

Following the procedure of Example 1, 2 or 3, the following additionalcompounds of Formula II were prepared.

    ______________________________________                                        R.sup.4 R.sup.5            Melting Point, °C.                          ______________________________________                                        C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5    Oil                                                H       CH(CH.sub.3)C.sub.3 H.sub.7                                                                      Oil                                                H       CH(CH.sub.3)C.sub.2 H.sub.5                                                                      77-78                                              H       CH[CH(CH.sub.3).sub.2 ].sub.2                                                                    Oil                                                H       CH(C.sub.2 H.sub.5)C.sub.3 H.sub.7                                                               27-28                                              H       CH.sub.3           118-120                                            C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7  Oil                                                H       CH(C.sub.2 H.sub.5).sub.2                                                                        77-79                                              n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7  Oil                                                H       CH(CH.sub.3)CONHCH.sub.3                                                                         163, dec.                                          H       n-C.sub.3 H.sub.7  70-72                                              C.sub.2 H.sub.5                                                                       methallyl          46-48                                              ______________________________________                                    

EXAMPLE 4

A solution of 40 g. of3-chloro-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline, 10.5 g. ofcyanamide and 30 g. of triethylamine in 250 ml. of 3A ethanol was heatedunder reflux for 5 days. The solution was allowed to cool and was thenpoured over ice-water. The product which separated was recrystallizedfrom 3A ethanol-water to give 36 g. (71%) of3-cyanamino-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline,triethylamine salt, m.p. 135°-137° C. The structure was confirmed by theNMR and IR spectra and elemental analysis.

Calculated: C, 49.35; H, 6.32; N, 18.17; Found: C, 49.56; H, 6.06; N,18.37.

Following the procedure of Example 4, the following additional compoundsof Formula III were prepared. All were obtained as the triethylaminesalt.

    ______________________________________                                        R.sup.7                                                                             R.sup.8  R.sup.9        Melting Point, °C.                       ______________________________________                                        CN    n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                            102-103                                         CN    C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                              122-124                                         CN    H        n-C.sub.3 H.sub.7                                                                            130-131                                         CN    CH.sub.3 C.sub.2 H.sub.5                                                                              84-86                                           CN    CH.sub.3                                                                                ##STR11##      98-100                                         CN    CH.sub.3 CH.sub.2 C CH  129-132                                         CN    n-C.sub.3 H.sub.7                                                                       ##STR12##     68-70                                           ______________________________________                                    

The following cyanamino free bases were prepared by neutralizing thecorresponding triethylamine salts with dilute hydrochloric acid indiethyl ether at room temperature.

    ______________________________________                                        R.sup.7  R.sup.8  R.sup.9     Melting Point, ° C.                      ______________________________________                                        CN       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                           195-198                                         CN       H        CH(C.sub.2 H.sub.5).sub.2                                                                 106-110                                         CN       H        n-C.sub.3 H.sub.7                                                                         140-143                                         ______________________________________                                    

EXAMPLE 5

To a cold solution of 40 g. of3-chloro-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline in 400 ml. ofdimethylformamide was added 36 g. of sodium sulfide nonahydrate in 100ml. of water. The mixture was stirred for one-half hour and cyanogenchloride was bubbled into the cold solution for 10 minutes. The darksolution became light red. The reaction mixture was poured overice-water and the solid product separated. Recrystallization from 3Aethanol-water gave 39 g. (89%) of2,6-dinitro-N-(3-pentyl)-3-thiocyanato-4-trifluoromethylaniline, m.p.97°-99° C. The structure was confirmed by the NMR spectrum and elementalanalysis.

Calculated: C, 41.27; H, 3.46; N, 14.81; Found: C, 41.02; H, 3.40; N,14.56.

Following the procedure of Example 5, the following additional compoundsof Formula VIII were prepared.

    ______________________________________                                        Q     R.sup.23 R.sup.24       Melting Point, °C.                       ______________________________________                                        SCN   H        CH.sub.3       125-126                                         SCN   CH.sub.3 CH.sub.3       153-155                                         SCN   H        N(CH.sub.3).sub.2                                                                            146-148                                         SCN   n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                            Oil                                             SCN   C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                              116-118                                         SCN   CH.sub.3                                                                                ##STR13##     75-76                                           SCN   CH.sub.3 CH.sub.2CH     84-86                                           SCN   C.sub.2 H.sub.5                                                                         ##STR14##     92-94                                           ______________________________________                                    

The preparation of 3-cyanomethylthio compounds is illustrated by thefollowing example.

EXAMPLE 6

A mixture of 3.4 g. of3-chloro-N,N-diethyl-2,6-dinitro-4-trifluoromethylaniline and 2.4 g. ofsodium sulfide nonahydrate in dimethyl sulfoxide was stirred for onehour at 0° C. Chloroacetonitrile (0.76 g.) was added and the mixture wasstirred overnight at room temperature. The reaction mixture was pouredover ice and extracted with ether. The ether was evaporated and theresidue was recrystallized twice from ethanol to yield 2.7 g. of3-cyanomethylthio-N,N-diethyl-2,6-dinitro-4-trifluoromethylaniline, m.p.77°-79° C. The structure was confirmed by the NMR spectrum.

EXAMPLE 7

To a cold solution of 3.6 g. of3-chloro-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline and 1.1 g. ofmethyl thioglycolate in 75 ml. of dimethylformamide was added dropwise6.6 g. of potassium hydroxide in 5 ml. of water. The mixture was allowedto come to room temperature and stirred for one hour. The reactionmixture was poured over ice water and the product solidified. It wasrecovered by filtration and recrystallized from ethanol to yield 1.6 g.of2,6-dinitro-N-(3-pentyl)-3-methoxycarbonylmethylthio-4-trifluoromethylaniline,m.p. 60°-61° C. The structure was confirmed by the NMR spectrum andelemental analysis.

Calculated: C, 42.35; H, 4.27; N, 9.88; Found: C, 42.43; H, 4.14; N,9.89.

EXAMPLE 8

To a cold solution of 6.0 g. of3-chloro-2,6-dinitro-N-methyl-4-trifluoromethylaniline and 4.0 ml. ofβ-mercaptopropionitrile in 100 ml. of dimethylformamide was addedportionwise, with stirring 0.6 g. of lithium hydroxide. The solution waswarmed to 25° C. and stirred for 12 hours. The reaction mixture waspoured over ice water and the product solidified. It was recovered byfiltration and recrystallized from ethanol to yield 5.8 g. of3-cyanoethylthio-2,6-dinitro-N-methyl-4-trifluoromethylaniline, m.p.116°-117° C. The structure was confirmed by the NMR spectrum andelemental analysis.

Calculated: C, 37.72; H, 2.59; N, 16.00; Found: C, 37.96; H, 2.84; N,16.29.

EXAMPLE 9

To a cold solution of 21.3 g. of3-chloro-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline and 10 ml. ofβ-mercaptopropionitrile in 200 ml. of dimethylformamide was addedportionwise 2.0 g. of lithium hydroxide. The mixture was warmed to 25°C. and stirred for 2 hours. The reaction mixture was poured over icewater and the product oiled out. The solution was extracted with ether,washed with water, dried and concentrated to leave an oil. The productwas chromatographed on a silica-gel column with benzene and the solventwas removed to yield 2.0 g. of3-cyanoethylthio-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline. Thestructure was confirmed by the NMR spectrum and elemental analysis.

Calculated: C, 44.33; H, 4.22; N, 13.79; Found: C, 44.29; H, 4.22; N,13.63.

EXAMPLE 10

To a cold solution of 1.7 g. (0.01 mole) of silver nitrate in 150 ml. ofmethanol there was added portionwise 6.0 g. (0.01 mole) ofbis[4-di(n-propyl)amino-3,5-dinitropheyl]disulfide [prepared as taughtby Cannon, U.S. Pat. No. 3,725,479 (Apr. 3, 1973)]. When the additionwas complete, gaseous ammonia was bubbled into the solution for about 4hours and an additional 0.5 g. of silver nitrate was added. Thin layerchromatography showed that there was a slight amount of startingmaterial still remaining. The reaction mixture was stirred overnight atroom temperature. The reaction mixture was then cooled and concentratedin vacuo. The residue was taken up in benzene and filtered. The solidmaterial collected on the filter was washed with ether. The filtrate wasconcentrated in vacuo to leave a red oil, which solidified. The productweighed 2.4 g. and had a melting point of about 63°-65° C. It wasidentified by elemental analyses and NMR and IR spectra as4-(dipropylamino)-3,5-dinitrobenzene sulfenamide.

Calculated: C, 45.85; H, 5.77; N, 17.82; S, 10.20; Found: C, 45,59; H,5.50; N, 17.62; S, 9.90.

EXAMPLE 11

To a solution of 1 g. (0.003 mole) of4-(dipropylamino)-3,5-dinitrobenzenesulfenamide in 50 ml. of methylenechloride, there was added 0.56 g. (0.0032 mole) of m-chloroperbenzoicacid. The reaction mixture became slightly warm and it was stirred forabout 15 minutes at ambient room temperature. Thin layer chromatographyshowed no starting material remained. The reaction product mixture wasextracted twice with dilute aqueous sodium bicarbonate solution and thenwashed once with water. The washings were discarded and the organiclayer was concentrated in vacuo to leave an oil which was eluted from asilica gel column with 1:1 ethyl acetate:hexane solvent. The firstproduct obtained from the column was a disulfide compound. The secondproduct isolated from the column was recrystallized from 95 percentethanol to yield product having a melting point of about 125°-126°C.,and was identified by elemental analyses and NMR spectrum as4-(dipropylamino)-3,5-dinitrobenzenesulfinamide. Weight: 550 mg.

Calculated: C, 43,63; H, 5.49; N, 16.96; Found: C, 43.89; H, 5.31; N,16.68.

EXAMPLE 12

A mixture of 5.5 g. (0.02 mole) of 4-bromo-2,6-dinitroanisole and 5 ml.of 3-aminopentane was stirred at room temperature for about 4 hours. Atthe end of that time, thin layer chromatography showed no startingmaterial remained. The reaction product mixture was cooled over theweekend in the refrigerator and then concentrated in vacuo to leave aresidual oil, which solidified on standing. This product was identifiedby elemental analyses and NMR spectrum as4-bromo-N-(1-ethylpropyl)-2,6-dinitroaniline. Weight: 7.0 g.

Calculated: C, 39.78; H, 4.25; N, 12.65; Found: C, 40.05; H, 4.18; N,12.85.

EXAMPLE 13

To a cold solution of 5.0 g. of3-chloro-2,6-dinitro-N-(3-pentyl)-4-trifluoromethylaniline in 75 ml. ofdimethylformamide was added 10 ml. methylmercaptan. To the mixture wasthen added a solution of 5.0 g. of potassium hydroxide in 20 ml. ofwater portionwise. The reaction mixture was warmed to ambient roomtemperature and stirred for about 1/2 hour. The reaction mixture wasthen poured over a mixture of ice and water. The precipitate whichseparated crystallized on standing overnight. The precipitate wasfiltered off and dried. It had a melting point of about 39°-41° C. andwas identified by elemental analyses and NMR spectrum as2,6-dinitro-N-(3-pentyl)-3-methylmercapto-4-trifluoromethylaniline. Theproduct weighed 4.0 g.

Calculated: C, 42.51; H, 4.39; N, 11.44; Found: C, 42.59; H, 4.31; N,11.29.

EXAMPLE 14

To a cold solution (0° C.) of 3.5 g. of3-chloro-2,6-dinitro-N,N-diethylaniline in 60 ml. of dimethylformamide,there was added dropwise a solution of 3.4 g. of sodium monosulfidenonahydrate in 10 ml. of water. After addition was complete, thin layerchromatography of the reaction mixture showed little starting materialremained. There was then added to the reaction mixture an excess ofchloroacetonitrile at room temperature. The reaction mixture was stirredat room temperature for about 6 hours and then poured over crushed ice.The aqueous mixture was filtered and the solid which was recovered waschromatographed over a silica gel column using benzene as the eluent.There was isolated product having a melting point of about 63°-65° C.and identified by elemental analyses and NMR spectrum as[[3-(diethylamino)-2,4-dinitrophenyl]thio]acetonitrile.

Calculated: C, 46.44; H, 4.55; N, 18.05; Found: C, 46.29; H, 4.30; N,18.05.

Tests against fungal foliar phytopathogens have demonstrated thepowerful plant protective effect of the compounds of this invention. Thefirst series of tests to be described exemplify the use of the compoundsto reduce both the incidence and severity of grape downy mildew. In thetests described below, the compounds were applied as a solution oremulsion prepared by mixing 70 mg. of test compound with 1.925 ml. of amixture prepared from 500 ml. of acetone, 500 ml. of ethanol and 100 ml.of polyoxyethylene sorbitan monolaurate. The composition containing thetest compound was then diluted with deionized water to obtain thedesired concentration, measured in parts per million by weight (ppm.).

In the tests, the host plant was Vitis vinifera. The pathogen employedwas Plasmopara viticola. Stock grape plants were grown in a greenhouseto serve as a supply of leaves for test use. On the test day, youngexpanding leaves were detached from the vines. One leaf was placedbottom side up in a plastic petri plate (100×20 mm.) and a water-soakedwad of cotton was wrapped around the petiole base. The petri platecontained a Whatman filter paper placed on top of an expanded plasticmat. The mat and filter paper kept the leaf above water flooding thebottom of the petri plate. Each test chemical was sprayed on the underside of the leaf and allowed to dry. All the test leaves were theninoculated by atomizing a conidial suspension over the under leafsurface and then each plate was covered. All the plates were placed on ashelf in a mist room at a temperature of 18°-20° C. and a light/darkcycle of 8/16 hours. Illumination was obtained from cool whitefluorescent lamps ranging between 850-1000 foot-candles. Seven daysafter treatment, the leaves were examined and symptoms of disease wereobserved and results recorded using a scale of 1 to 5, wherein 1indicates severe disease or no control and 5 indicates no disease orcomplete control.

The conidia employed as the inoculum for the test were obtained fromrecently infected leaf tissue stored in a chillroom at 5° C. The conidiawere washed off the leaf surface with a brush and suspended in deionizedwater. The suspension was sprayed on leaf surfaces with a DeVilbissatomizer.

In each test, two non-treated control leaves were sprayed with watercontaining the solvent-surfactant system. In addition, one leaf wassprayed with the commercial fungicide, manganeseethylene-1,2-bisdithiocarbamate (maneb).

The results obtained with a number of compounds of this invention aresummarized in the following table. A wide range of concentrations of thetest compounds was employed. A blank space in the table indicates thatthe compound was not tested at the indicated concentration. An asteriskindicates that the compound was phytotoxic at the indicatedconcentration. When a compound was tested more than once at the sameconcentration, the result given is an average. The 3-cyanamino compoundswere tested as the triethylamine salt. Testing of3-cyanamino-N,N-diethyl-2,6-dinitro-4-trifluoromethylaniline as thetriethylamine salt and the free compound showed both forms performedessentially the same.

                                      TABLE 1                                     __________________________________________________________________________     ##STR15##                                                                                                              Downy Mildew Control (ppm.)         Q.sup.1     Q.sup.2 R       R°     800                                                                              400                                                                              200                                                                              100                                                                              50 25 12.5              __________________________________________________________________________    CF.sub.3    H       H       n-C.sub.3 H.sub.7                                                                           4  3- 1                             CF.sub.3    H       H       CH(CH.sub.3)CH(CH.sub.3)C.sub.2 H.sub.5                                                     4+ 2+ 1                             CF.sub.3    H       H       CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)C.sub.2                                      H.sub.5       3  3- 3                             CF.sub.3    H       H       CH(CH.sub.3)CH.sub.2 CH.sub.2 CH(CH.sub.3).sub                                .2            2  2+ 1                             CF.sub.3    H       H       n-C.sub.5 H.sub.11                                                                          3+ 1  1                             CF.sub.3    H       H       n-C.sub.6 H.sub.13                                                                          4+ 2  2                             CF.sub.3    H       H       CH.sub.2 CH(CH.sub.3).sub.2                                                                 3+ 1  2+                            CF.sub.3    H       H       CH(CH.sub.3)C.sub.2 H.sub.5                                                                 1  2  3                             CF.sub.3    H       H       CH(CH.sub.3)C.sub.5 H.sub.11                                                                2  3- 2+                            CF.sub.3    H       H       CH(CH.sub.3)C.sub.4 H.sub.9                                                                 5  4  3+                            CF.sub.3    H       H       CH(CH.sub.3)C.sub.3 H.sub.7                                                                 3- 4  1                             CF.sub.3    H       H       CH(C.sub.2 H.sub.5).sub.2                                                                   4  4+ 2                             CF.sub.3    H       H       CH(CH.sub.3)CH(CH.sub.3).sub.2                                                              2  1  3                             CF.sub.3    H       H       N(C.sub.3 H.sub.7).sub.2                                                                    2  4  2+                            CF.sub.3    H       C.sub.2 H.sub.5                                                                       CH.sub.2 CH.sub.2 CHClCH.sub.3                                                              4  1  2+                            CF.sub.3    H       H                                                                                      ##STR16##    1  1  2                             CF.sub.3    H       H       CH(CH.sub.3)CH.sub.2 OH                                                                     5  4+ 1                             CF.sub.3    H       H                                                                                      ##STR17##    5  4+ 1                             CF.sub.3    H       H       N(C.sub.2 H.sub.5).sub.2                                                                    5  4+ 4+ 1  3  3+                   CF.sub.3    H       H                                                                                      ##STR18##    3+ 5  5                             CF.sub.3    H       H                                                                                      ##STR19##    5  5  3+ 3+ 4  4+                   CF.sub.3    H       H                                                                                      ##STR20##    5  1  1                             CF.sub.3    H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           5  5  4+ 3- 2+ 1                    CF.sub.3    H       n-C.sub.3 H.sub.7                                                                     C.sub.2 H.sub.4 Cl                                                                          5  5  5  4+ 1                       CF.sub.3    H       n-C.sub.3 H.sub.7                                                                     cyclopropylmethyl                                                                           5  5  5  5  4-                      CF.sub.3    H       C.sub.2 H.sub.5                                                                       methallyl     1+ 4  1+ 2- 1                       CF.sub.3    Cl      CH.sub.3                                                                              CH.sub.3      5  5  1+ 1  2-                      CF.sub.3    Cl      H       CH.sub.3      5  5  3+ 1  1                       CF.sub.3    Cl      H       CH(CH.sub.3)C.sub. 2 H.sub.5                                                                3  3  2  1  3+                      CF.sub.3    Cl      C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                                                                           *  3+ 1  3+ 1                       CF.sub.3    Cl      n-C.sub.3 H.sub.7                                                                     methallyl     *  3- 2  2  2-                      CF.sub.3    Cl      n-C.sub.3 H.sub.7                                                                     allyl         *  4+ 4- 1  4+                      CF.sub.3    Cl      C.sub.2 H.sub.5                                                                       methallyl     4+ 3- 3+ 4+ 2-                      CF.sub.3    Cl      n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           *  2+ 4+ 2+ 4+                      CF.sub.3    Cl      H       N(CH.sub.3).sub.2   3  2  4- 4                    CF.sub.3    N.sub.3 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             5  5  4+ 5  4- 3- 2+                CF.sub.3    N.sub.3 CH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                           5  5  4+ 3- 2+                      CF.sub.3    N.sub.3 H       CH(CH.sub.3)C.sub.2 H.sub.5                                                                 5  4+ 4+ 2+ 4+                      CF.sub.3    N.sub.3 H                                                                                      ##STR21##    4+ 2  3+ 3- 5                       CF.sub.3    N.sub.3 H       CH.sub.3      5  5  5  4+ 4+ 4- 3-                CF.sub.3    N.sub.3 H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  4  5  4  4  1+                CF.sub.3    N.sub.3 H       CH(C.sub.2 H.sub.5)C.sub.3 H.sub.7                                                          *  3+ 4+ 2  2                       CF.sub.3    N.sub.3 CH.sub.3                                                                              CH.sub.3      5  5  5  3  2- 4  4-                CF.sub.3    N.sub.3 C.sub.2 H.sub.5                                                                       n-C.sub.4 H.sub.9                                                                           5  5  4+ 4  2                       CF.sub.3    N.sub.3 C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                                                                           5  5  5  4  3  3- 3-                CF.sub.3    N.sub.3 C.sub.2 H.sub.5                                                                       methallyl     5  5  5  3  4  4- 3+                CF.sub.3    N.sub.3 n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           5  5  5  5- 4+ 3+ 4-                CF.sub.3    N.sub.3 H       N(CH.sub.3).sub.2                                                                           5  5  4  2+ 3+ 2                    CF.sub.3    N.sub.3 H       CH(CH.sub.3)CONHCH.sub.3                                                                    3+ 3- 3-                             ##STR22##                                                                                H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           5  5  5                             SO.sub.2 NS(CH.sub.3).sub.2                                                               H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           3  4  2-                            SO.sub.2 NH.sub.2                                                                         H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           5  5  5  5  5  4+                   SO.sub.2 CH.sub.3                                                                         H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           4+ 4+ 4+ 4+ 4+                      SO.sub.2 NCHN(CH.sub.3).sub.2                                                             H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           3  1  3-                             ##STR23##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7   4- 4- 4  1                     ##STR24##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7   4- 3  3+ 1                    SO.sub.2 NCHOC.sub.2 H.sub.5                                                              H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  4+ 4  3- 2+                    ##STR25##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7   4+ 1  1  1                    H           Cl      C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             5  4- 1  1  1                       H           NH.sub.2                                                                              C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             5  5  5  4+ 2+                      H           OCH.sub.3                                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             *  4  3+ 4  3-                      CH.sub.3    Cl      CH.sub.2 CH(CH.sub.3).sub.2                                                           methallyl     5  4+ 3+ 2- 4+                      CH.sub.3    Cl      n-C.sub.4 H.sub.9                                                                     methallyl     3- 5  3+ 2+ 2-                      CH.sub.3    Cl      H       CH(CH.sub.3)CONHCH.sub.3                                                                    5  4+ 5  4  4  2                    CH.sub.3    CH.sub.3                                                                              H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  4+ 4  2- 2-                   H           CH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           5  *  3                             CH(CH.sub.3).sub.2                                                                        H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           4  3+ 4  3- 3+                      C(CH.sub.3).sub.3                                                                         H       H       CH(CH.sub.3)C.sub.2 H.sub.5                                                                 5  4+ 4  3- 1                       CF.sub.3    OCH.sub.3                                                                             H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  4  4  3- 3- 2+                CF.sub.3    OCH.sub.3                                                                             n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           5  5  3+ 1  4+                      CF.sub.3    OCH.sub.3                                                                             C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             5  3+ 1  1  1                       CF.sub.3    OH      C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             5  5  4+ 4+ 3  1+ 2-                CF.sub.3    OCH.sub.3                                                                             H       CH.sub.3            4+ 4  2+ 1                    CF.sub.3    CH.sub.3                                                                              n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           4- 3- 1+                            CF.sub.3    CO.sub.2 H                                                                            n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           3  2  4-                            CF.sub.3    CONH.sub.2                                                                            H       CH(C.sub.2 H.sub.5).sub.2                                                                   4+ 4  3+                            CF.sub.3    CN      n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           4- 3+ 4-                            CF.sub.3    CONH.sub.2                                                                            C.sub.2 H.sub.5                                                                       n-C.sub.4 H.sub.9                                                                           5  4  4                             CF.sub.3    OCH.sub.3                                                                             CH.sub.3                                                                              CH.sub.3      5  5  2-                            CF.sub.3    SCH.sub.3                                                                             H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  4+ 4+ 3  4  4+                CF.sub.3    SCN     H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  5  4+ 3  1+ 2                 CF.sub.3    SCH.sub.2 CO.sub.2 CH.sub.3                                                           H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  2  *  4+ 1+                      CF.sub.3    SCH.sub.2 CH.sub.2 CN                                                                 H       CH.sub.3      1+ 3  1                             CF.sub.3    SCH.sub.2 CN                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             2  3+ 4  3+                         CF.sub.3    SCN     H       CH.sub.3      5  4+ 3  2+ 2- 2-                   CF.sub.3    SCH.sub.2 CH.sub.2 CN                                                                 H       CH(C.sub.2 H.sub.5).sub.2                                                                   4  4  4- 1                          CF.sub.3    SCN     CH.sub.3                                                                              CH.sub.3      5  4+ 3+                            CF.sub.3    SCN     H       N(CH.sub.3).sub.2                                                                           3+ 3  3-                            CF.sub.3    SCN     n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  4  2+ 1                       CF.sub.3    SCN     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5  1  1  2+ 1                       CF.sub. 3   NHCH.sub.3                                                                            H       CH.sub.3      4- 4- 2  1  3                       CF.sub.3    NHCN    H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  4+ 4+ 4+ 3                    CF.sub.3    NHCN    n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7   4- 2+ 3  1                    CF.sub.3    NH.sub.2                                                                              H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  4+ 5  5  5  2+                CF.sub.3    NH.sub.2                                                                              n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           5  5  4+ 4  4  4- 3+                CF.sub.3    NH.sub.2                                                                              C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             5  5  5  5  5  5  4+                CF.sub.3    NH.sub.2                                                                              C.sub.2 H.sub.5                                                                       methallyl     5  5  5  5  4+ 4+ 3+                CF.sub.3    NH.sub.2                                                                              CH.sub.3                                                                              CH.sub.3      5  5  5  4+ 3- 3-                   CF.sub.3    NH.sub.2                                                                              H       CH.sub.3      2+ 1  2+ 2                          CF.sub.3    NH.sub.2                                                                              H       N(CH.sub.3).sub.2                                                                           5  4+ 4+ 4+ 4+ 3                    CF.sub.3    NH.sub.2                                                                              H       CH(C.sub.2 H.sub.5)C.sub.3 H.sub.7                                                          2- 2+ 3                             CF.sub. 3   NH.sub.2                                                                              H       CH(CH.sub.3)C.sub.3 H.sub.7                                                                    3- 2+ 4- 2+                      CF.sub.3    H       H       N(CH.sub.3).sub.2                                                                           5  4  3-                            CF.sub.3    H       H                                                                                      ##STR26##    4+ 3  4                             CF.sub.3    NHCN    H       n-C.sub.3 H.sub.7                                                                              1+ 2  1                          SO.sub.2 N.sub.3                                                                          H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  5                          SO.sub.2 N(CH.sub.3)OCH.sub.3                                                             H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              3+ 3+ 1                          SO.sub.2 NH.sub.2                                                                         H       CH.sub.3                                                                              C.sub.2 H.sub.5  4+ 4  3+                         SO.sub.2 NH.sub.2                                                                         H       H       CH(C.sub.2 H.sub.5).sub.2                                                                      5  5  5                          SO.sub.2 NHNH.sub.2                                                                       H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4- 3  1                          SO.sub.2 N(CH.sub.3).sub.2                                                                H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              2+ 2  1                          SO.sub.2 NHCH.sub.3                                                                       H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              3+ 3  3-                         SO.sub.2 NH.sub.2                                                                         H       C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5  4+ 5  4                          SO.sub.2 N(CH.sub.3)OH                                                                    H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4- 4- 2                          SO.sub.2 NHOCH.sub.3                                                                      H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  4+                         SO.sub.2 NH.sub.2                                                                         H       C.sub.2 H.sub.5                                                                       methallyl        5  4+ 4+                         SO.sub.2 NH.sub.2                                                                         H       C.sub.2 H.sub.5                                                                        ##STR27##       4+ 5  4+                         CF.sub.3    NHCOCH.sub.3                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             4+ 4+ 4                             CF.sub.3    Cl      H       n-C.sub.3 H.sub.7                                                                           4  4+ 4                             CF.sub.3    Cl      CH.sub.3                                                                              C.sub.2 H.sub.5                                                                             1  1  1                             CF.sub.3    SCN     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                             5  4- 1                             CF.sub.3    NHCN    C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5  5  4+ 4+                         CF.sub.3    H       CH.sub.2 CH.sub.2 Cl                                                                  CH.sub.2 CH.sub.2 Cl                                                                        2+ 4- 3-                            CF.sub.3    H       C.sub.2 H.sub.5                                                                       CH.sub.2 CH.sub. 2 OH                                                                       5  3  3-                            CF.sub.3    H       C.sub.2 H.sub.5                                                                        ##STR28##    5  4+ 3+ 1  1  1                    CF.sub.3    H       n-C.sub.3 H.sub.7                                                                     CH.sub.2 CHCH.sub.2                                                                         4- 2- 2+                            CF.sub.3    H       n-C.sub.3 H.sub.7                                                                      ##STR29##    5  5  3+ 1  1  1                     ##STR30##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  4+ 4- 4+ 4+ 4                  ##STR31##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  4+ 4+ 4+ 3+                 ##STR32##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  4+ 5  4  4+                 ##STR33##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  4  4+ 4+ 3+                 ##STR34##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              3- 3+ 4-                          ##STR35##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  4+ 4+ 4+ 4  2                  ##STR36##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              2+ 2+ 4                           ##STR37##  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub. 7                                                                             5  4+ 4+ 5  4+ 4                 SO.sub.2 NH.sub.2                                                                         H       CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                            4+ 1  1                          SO.sub.2 N.sub.3                                                                          H       CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                            4+ 4  1                          SO.sub.2 NHOCH.sub.3                                                                      H       CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                            4+ 4- 3+                         SO.sub.2 NS(C.sub.2 H.sub.5).sub.2                                                        H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              2  1  1                          SO.sub.2 NS(CH.sub.3)C.sub.2 H.sub.5                                                      H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4  2  4                          SO.sub.2 NHSC.sub.6 H.sub.5                                                               H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  3  2- 2- 2                 SO.sub.2 NS(CH.sub.3)C.sub.6 H.sub.5                                                      H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4+ 2+ 1                          SO.sub.2 NS(C.sub.6 H.sub.5).sub.2                                                        H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              1  1  4-                         SO.sub.2 NS(CH.sub.2 C.sub.6 H.sub.5).sub.2                                               H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              3+ 2+ 2+                         CF.sub.3    SCN     CH.sub.3                                                                               ##STR38##       4- 1  1                          C(CH.sub.3).sub.2 CN                                                                      H       C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5  3  2- 3                          SO.sub.2 NC(C.sub.2 H.sub.5)OC.sub.2 H.sub.5                                              H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  4  4+ 4  2+                SO.sub.2 NC(C.sub.6 H.sub.5)OCH.sub.3                                                     H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4+ 4+ 3  4+ 1  1                 CF.sub.3    H       CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                                                                         4  4  2                             CF.sub.3    H       CH.sub.2 CH.sub.2 CN                                                                  CH.sub.2 CH.sub.2 CN                                                                        3- 4  4-                            CH.sub.3    H       CH.sub.2 CH.sub.2 Cl                                                                  CH.sub.2 CH.sub.2 Cl                                                                        4  3- 5                             CH.sub.3    H       CH.sub.2 CH.sub.2 OH                                                                  CH.sub.2 CH.sub.2 OH                                                                        4+ 4+ 1                             CF.sub.3    H       n-C.sub.3 H.sub.7                                                                     CH.sub. 2 CH.sub.2 OH                                                                       5  5  4+ 4+ 4+ 4-                   C(CH.sub.3).sub.2 CN                                                                      H       H       CH(CH.sub.3)C.sub.2 H.sub.5                                                                    4+ 3+ 2+                         CF.sub.3    SCN     CH.sub.3                                                                              CH.sub.2 CCH     2+ 4- 2-                         C(CH.sub.3).sub.3                                                                         H       n-C.sub.3 H.sub.7                                                                      ##STR39##    3  2- 1                             CH.sub.2 CN H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           4+ 4- 4-                            SO.sub.3 CH.sub.3                                                                         H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4+ 2+ 2                          SO.sub.2 NH.sub.2                                                                         H       C.sub.3 H.sub.7                                                                       cyclopropylmethyl                                                                              5  5  4+ 4  3- 2+                SO.sub.2 NH.sub.2                                                                         H       CH.sub.3                                                                              CH(CH.sub.3)C.sub.3 H.sub.7                                                                    4+ 4+ 4- 2- 1+                   SO.sub.2 NH.sub.2                                                                         H       CH.sub.2 CHCH.sub.2                                                                    ##STR40##       5  5  4  2+ 3- 4-                SO.sub.2 NH.sub.2                                                                         H       n-C.sub.3 H.sub.7                                                                     CH.sub.2 CH(CH.sub.3).sub.2                                                                    5  5  4  2  3- 4                 SO.sub.2 Cl H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4+ 2  1                          CF.sub.3    NHCN    CH.sub.3                                                                              CH.sub.2 CCH     4+ 4  2-                         CF.sub.3    NHCN    CH.sub.3                                                                               ##STR41##       4+ 4  1                          CF.sub.3    NHCN    n-C.sub.3 H.sub.7                                                                      ##STR42##       4  1+ 1                          SO.sub.2 N(CH.sub.3)SCCl.sub.3                                                            H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4- 3+ 4-                         SO.sub.2 NC(CH.sub.3)OC.sub.4 H.sub.9                                                     H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  3  1  1  2                 SO.sub.2 NC(C.sub.6 H.sub.5)OC.sub.2 H.sub.5                                              H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  3  3- 1  1                 SO.sub.2 NHOC.sub.4 H.sub.9                                                               H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4  4  3+                         SO.sub.2 NC(C.sub.2 H.sub.5)OCH.sub.3                                                     H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4+ 5  2+ 1  1  2                 SO.sub.2 NH.sub.2                                                                         H       CH.sub.3                                                                              cyclopentyl      4+ 4+ 3  1  3- 1                 SO.sub.2 NHCH.sub.3                                                                       H       n-C.sub.3 H.sub.7                                                                     cyclopropylmethyl                                                                              1  2- 2-                         Cl          H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                           4+ 3+ 3-                            SO.sub.2 NHOH                                                                             H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4- 4+ 2+                         SNH.sub.2   H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              4- 2+ 3-                         SONH.sub.2  H       n-C.sub.3 H.sub.7                                                                     n-C.sub.3 H.sub.7                                                                              5  5  5                          Br          H       H       CH(C.sub.2 H.sub.5).sub.2                                                                      4+ 4+ 4+                         CF.sub.3    SCH.sub.3                                                                             H       CH(C.sub.2 H.sub.5).sub.2                                                                   5  5  4+ 4+ 4+                      H           SCH.sub.2 CN                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub. 5 3- 2  1                          __________________________________________________________________________

The following series of tests illustrates the use of this invention toprotect plants from late blight. The host plants in these tests weretomatoes growing in field plots, and were naturally infected with lateblight (Phytophthora infestans).

The compounds used in these tests were formulated as 25 percent wettablepowders, and were dispersed for application in water to produce activeingredient concentrations, in ppm., named in the table below. Alldispersions were applied at the rate of 1400 liters/hactare.

When the test began, the plants were about 6 weeks old. The testcompounds were applied seven times at intervals of about seven days.Disease control was rated four times at 4-5 day intervals, beginning atthe end of the series of spray applications.

Late blight incidence in the untreated control plots was 27 percent atthe first observation, increasing to over 80 percent at the lastobservations.

Disease control achieved by the test compounds is reported below aspercent control, compared to untreated controls.

                                      TABLE 2                                     __________________________________________________________________________     ##STR43##                                                                                                   Late Blight Control                                                           Observation                                    Q'          R'     R"  Concentration                                                                         1st                                                                             2nd                                                                              3rd                                                                              4th                                    __________________________________________________________________________     ##STR44##  n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                  50 100 300                                                                           80 89 90                                                                        58 59 79                                                                         52 56 77                                                                         23 33 47                               NC(CH.sub.3)OCH.sub.3                                                                     n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                  50     72                                                                              48 23 30                                                            100     90                                                                              78 67 40                                                            300     87                                                                              80 82 77                                     N.sub.3     n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                  50     70                                                                              52 19 47                                                            100     90                                                                              74 63 65                                                            300     74                                                                              72 67 70                                     NH.sub.2    n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                  50     78                                                                              67 52 68                                                            100     70                                                                              77 68 65                                                            300     91                                                                              83 84 67                                     NH.sub.2    n-C.sub.3 H.sub.7                                                                    C.sub.2 H.sub.5                                                                    50     65                                                                              57 53 23                                                            100     77                                                                              74 72 53                                                            300     86                                                                              76 72 57                                     NH.sub.2                                                                                   ##STR45##                                                                           C.sub.2 H.sub.5                                                                    50 100 300                                                                           86 52 81                                                                        81 67 80                                                                         49 65 62                                                                         43 47 53                               __________________________________________________________________________

As will be noted from the data in the above tables, compounds of FormulaII are preferred compounds of this invention. Especially preferredcompounds of Formula II are those wherein both R⁴ and R⁵ are n-propyl,R⁴ is hydrogen and R⁵ is methyl, R⁴ is hydrogen and R⁵ is 3-pentyl.

Another preferred group of compounds for use in the method of thisinvention are the compounds of Formula V. Of the compounds of Formula V,the most preferred compounds are those wherein X is N₃, NH₂, CH₃,N═C(R¹⁹)OR²⁰, or N(R¹⁸)CH₂ Het, and both R¹⁴ and R¹⁵ are independentlyethyl, n-propyl or 2-chloroallyl.

A third class of preferred compounds are those of Formula III andparticularly those wherein R⁷ is hydrogen or cyano. Especially preferredis the compound wherein R⁷ is hydrogen and both R⁸ and R⁹ are ethyl aswell as the compound wherein R⁷ is hydrogen, R⁸ is hydrogen and R⁹ is3-pentyl. Another preferred compound of this group is the one in whichR⁷ is cyano, R⁸ is hydrogen and R⁹ is 3-pentyl.

Another group of preferred compounds are those of Formula I wherein R¹is n-propyl and R² is n-propyl, 2-chloroethyl or cyclopropylmethyl.Another preferred compound is the compound of Formula VIII wherein Q isthiocyanato, R²⁷ is hydrogen and R²⁸ is 3-pentyl.

In accordance with standard agricultural practices the2,6-dinitroanilines to be employed in the presently claimed method arepreferably employed in liquid, powder or dust compositions containingone or more of the active compounds. In preparing such compositions, the2,6-dinitroaniline compounds can be modified with one or more of aplurality of additaments including organic solvents, petroleumdistillates, water or other liquid carriers, surface active dispersingagents and finely divided inert solids. In such compositions, thedinitroaniline compound can be present in a concentration from about 2to 98% by weight.

In the preparation of dust compositions, the dinitroanilines can becompounded with any of the finely divided solids such as pyrophyllite,talc, chalk, gypsum and the like. In such operations, the finely dividedcarrier is ground or mixed with the dinitroaniline or is wet with asolution of the dinitroaniline in a volatile organic solvent. Similarly,dust compositions containing the active compound can be prepared withvarious solid surface active dispersing agents, such as fuller's earth,bentonite, attapulgite and other clays. Depending upon the proportionsof ingredients, these dust compositions can be employed as concentratesand subsequently diluted with an additional solid surface activedispersing agent or with pyrophyllite, chalk, talc, gypsum and the liketo obtain the desired amount of active ingredient in a compositionadapted to be employed for the control of phytopathogens. Also, suchdust compositions can be dispersed in water with or without the aid ofdispersing agents to form liquid sprayable mixtures.

The dinitroaniline compounds or a liquid or dust concentrate compositioncontaining the active compound can be incorporated in intimate mixturewith surface active dispersing agents, such as nonionic emulsifyingagents, to form spray compositions. Such compositions may be employed assuch or may be dispersed in liquid carriers to form diluted sprayscontaining the active compound in any desired amount.

Similarly, the active dinitroaniline compounds can be compounded with asuitable water immiscible organic liquid and a surface active dispersingagent to produce emulsifiable concentrates which can be further dilutedwith water and/or oil to form spray mixtures in the form of oil-wateremulsions. Preferred dispersing agents to be employed in thesecompositions are oil soluble and include the nonionic emulsifiers, suchas condensation products of alkylene oxides with phenols, sorbitanesters, complex ether alcohols and the like. Suitable organic liquidswhich can be employed include petroleum oils and distillates, tolueneand synthetic organic oils. The surface active dispersing agents areusually employed in liquid compositions in the amount from 0.1 to 20% byweight of the composition.

The formulation of agricultural chemicals is a well-developed art andthose skilled in the art will have no difficulty in preparingformulations of active dinitroaniline compounds for use in the practiceof the method of this invention.

The exact concentration of the dinitroaniline compound for use in thecontrol of phytopathogens can vary widely provided that an effectiveamount is applied to the host plant. The amount which is effective isdependent upon the particular compound employed and the severity of theinfection. In general, good results are obtained using liquidcompositions containing from about 2,000 to about 10 ppm. of the activecompound. When dusts are used, good results are usually obtained withcompositions containing from about 0.05 to 5.0% or more by weight of theactive compound. Preferably, the compounds are applied at a rate ofabout 10 g. to about 2 kg. per hectare.

We claim:
 1. A method for reducing the incidence and severity of grapedowny mildew which comprises applying to the foliage of the host plant afungicidally-effective amount of a dinitroaniline compound having one ofthe following formulae: ##STR46## wherein R¹ is H, C₂ -C₃ alkyl,chloroethyl, cyanoethyl, C₃ -C₄ alkenyl or halo C₃ -C₄ alkenyl;when R¹is H, R² is N(R³)₂, normal C₃ -C₆ alkyl, branched C₄ -C₇ alkylcontaining no tertiary carbon atoms, 1-hydroxy-2-propyl or methallyl;when R¹ is not H, R² is 3-chloro-n-butyl, C₃ -C₄ alkenyl, halo C₃ -C₄alkenyl, chloroethyl, cyclopropylmethyl, cyanoethyl, hydroxyethyl, n-C₃H₇, or epoxypropyl; each R³ is independently C₁ -C₃ alkyl; ##STR47##wherein R⁷ is H, CN, C₁ -C₃ alkyl or C₂ -C₃ alkanoyl;R⁸ is H or C₁ -C₃alkyl; when R⁸ is H, R⁹ is N(R¹⁰)₂, C₁ -C₆ normal or branched alkylcontaining no tertiary carbon atoms, or C₃ -C₄ alkenyl; when R⁸ is C₁-C₃ alkyl, R⁹ is C₁ -C₃ alkyl, halo C₃ -C₄ alkenyl, propargyl or C₃ -C₄alkenyl; and each R¹⁰ is independently C₁ -C₃ alkyl; ##STR48## whereinR¹¹ is H or C₁ -C₃ alkyl;when R¹¹ is H, R¹² is N(R¹³)₂, C₁ -C₄ normal orbranched alkyl containing no tertiary carbon atoms, or C₃ -C₄ alkenyl;when R¹¹ is C₁ -C₃ alkyl, R¹² is C₁ -C₃ alkyl or C₃ -C₄ alkenyl; andeach R¹³ is independently C₁ -C₃ alkyl.
 2. A method as in claim 1wherein the dinitroaniline is a compound of Formula IV.
 3. A method asin claim 1 wherein the dinitroaniline is a compound of Formula III. 4.The method of claim 3 wherein R⁷ is hydrogen and each of R⁸ and R⁹ isethyl.
 5. The method of claim 3 wherein R⁷ is hydrogen, R⁸ is hydrogenand R⁹ is 3-pentyl.
 6. The method of claim 3 wherein R⁷ is cyano, R⁸ ishydrogen and R⁹ is 3-pentyl.
 7. A method as in claim 1 wherein thedinitroaniline is a compound of Formula I.
 8. The method of claim 7wherein each of R¹ and R² is n-propyl.